Stabilized oil- and water-repellent composition



United States Patent U.S. Cl. 26029.4 5 Claims ABSTRACT OF THEDISCLOSURE The addition of a compound of the structure CHzCHzO) 1H Cn2n+1N -HZ (CH2CH20) H wherein n is 12 to 18, the sum of x and y is 20,each of x and y is at least 1, and Z is chloride or acetate, to a padbath for applying fiuorinated oiland Waterrepellent polymers to textilefabrics has been found to stabilize the bath against the undesirableinteraction of incompatible pad bath ingredients.

The present invention is directed to new surfactant adjuvants used tostabilize textile treating pad baths against the effect of foreign trampreagents. More specifically, the present invention is directed to newsurfactant adjuvants used to stabilize pad baths prepared for theapplication of fiuorinated oiland Water-repellent formulations totextile fabrics.

The pad bath formulations used to apply fiuorinated oil andwater-repellent resins to textiles contain a number of components inaddition to the fiuorinated resins themselves. Thus, one or more waterrepellents, permanent press resins, crease resistance resins, softeners,hand modifiers, antistatic agents, and the like may also be present inthe pad bath. Each of these ingredients is a separate commercialproduct, and may be combined with its own dispersing agent. "Inaddition, the water repellents and crease resistance resins usuallyrequire curing catalysts in the form of amine hydrochlorides or heavymetal salts such as magnesium, zinc, or aluminum salts. The fiuorinatedoiland water-repellent resins also require dispersing agents of theirown.

When these many ingredients, dispersing agents and catalysts are broughttogether in one bath, stability is usually a serious problem. First ofall, as is 'well known, dispersing agents occur in four generaltypes-cationic, anionic, nonionic, and amphoteric and a number of theseare not mutually compatible in the same system. For instance,instability exists when many anionic and cationic dispersing agents arecombined in the same bath. Further, several types of dispersing agentslose their effectiveness in the presence of metal salts and other curingcatalysts, thus causing coagulation to occur in the treating bath.Finally, textiles often contain wetting agents and metal salts remainingin the fabric from prior treatments. As these foreign tramp reagents arecarried by the textiles into the pad bath, stability is seriouslyreduced.

Pad bath instability with resulting coagulation has been observed in thepast when attempting to prepare certain formulations or to treatspecific manufacturers textiles. In an attempt to stabilize such baths,nonionic surfactants such as the long-chain alkyloxy or alkaryloxypolyethyleneoxyethanols (ethylene oxide reaction products of fattyalcohols or alkylphenols) have been added. Bath stability has not beenuniversally obtained with such additives, however.

3,438,925 Patented Apr. 15, 1969 There exists, therefore, a need for anew additive which will stabilize pad baths under a wide variety ofconditions which normally leads to bath coagulation. It is to this needthat the subject invention is directed.

More specifically, the present invention is directed to an improved padbath for applying oil and water repellents to textile fabrics, theimprovement being the addition to the bath of a stabilizing amount of acompound having the structure wherein n is from 12 to 18, the sum of xand y is from 10 to 20, and each of x and y is at least one, and Z is ananion selected from the group consisting of chloride and acetate.

The present invention is also directed to new compositions of mattercomprising:

(A) A fiuorinated oiland water-repellent polymer derived from monomerssuch as (1) CH C (CH CO CH CH R;

wherein R, is a C to C perfluoroalky, (2) an alkyl acrylate ormethacrylate, wherein the alkyl group contains from one to eighteencarbons, (3) N-methylolacrylamide, and (4) a hydroxyalkyl methacrylate,

(B) A non-fiuorinated polymer derived from monomers such as a C to Calkyl methacrylate and N-rnethylolacrylamide, and

(C) A stabilizing compound of the structure where n, x, y, and Z are asdefined above.

The hydrochloride and acetate salts described above are particularlyuseful in pad baths containing a wide variety of fiuorinated polymersand interpolymers derived from the monomers CHFC (CH CO CH CH R whereinR; is a pet-fiuorinated alkyl group having 'from 4 to 14 carbon atoms.Such polymers are usually interpolymers containing units from (1) a C toC alkyl methacrylate or C to C -alkyl acrylate and (2) N-methylolacrylamide in addition to the fiuorinated monomer. Thefiuorinated polymer is combined with nonfiuorinated polymers orcopolymers of alkyl methacrylates, for example, the copolymer of2-ethylhexyl methacrylate and N-methylolacrylamide. An aqueousdispersion of these polymers or other similar polymers, using at acationic dispersing agent dimethyloctadecylamine acetate, is thencombined with other adjuvants to form the pad bath. A typicalformulation of this type is disclosed in Belgian Patent 645,697,containing 0.04% nonylphenoxypoly(ethyleneoxy)ethanol, 0.04% tartaricacid, 1.5% dispersed polyethylene, 5.0% resin finish Aerotex M23 (awater-soluble melamineformaldehyde condensate), 0.5% magnesium chloride2.5% Phobotex f/t/c, a melamine formaldehyde condensate-paraffin waxdispersion (described more fully in US. Patent 2,783,231), and 3.33% ofthe fiuorinated and non-fiuorinated polymer mixture referred to above.The nonylphenol derivative is included in the bath as a stabilizer. Thefiuorinated polymer mixture consists of 40 parts fiuorinated polymer and60 parts methacrylic ester polymer, the fluorinated and ester polymersbeing those described hereinafter in the examples. Another typicaloiland waterrepellent formulation is described in French Patent1,414,110, differing only in that the methacrylic ester polymer iscross-linked. This cross-linked polymer is further described hereinafterin the examples.

While formulations of these types are quite useful and widely used fortreating textile fibers, the pad baths are sensitive to addition offurther foreign materials, particularly anionic surfactants or wettingagents and foreign metal salts. Although the mills using theseformulations do not purposely add such agents to the pad baths, thetextile fabrics being treated in the bath often contain considerableamounts of wetting agents such as long-chain alkyl sulfates or alkarylsulfonates and occasionally metal salts as residues from previoustreatments such as dyeing. These foreign agents are dissolved from thefabric into the bath, upsetting the dispersant balance and causing thebath to coagulate. In addition, mills will often use waterrepellentresins and adjuvants other than that indicated above which can and docause trouble, particularly since these other adjuvants may containdispersants or metal salt catalysts which upset the dispersant balanceof the oil and water repellent and lead to bath coagulation.

It is known in the art that, if both cationic and anionic dispersingagents are to be used in the same system, coagulation may hopefully beprevented by addition of a nonionic agent, particularly of thepolyethylene-oxide type. The nonylphenoxypoly(ethyleneoxy)ethanol usedin the above-described oiland water-repellent formulations was added forthat purpose. While such agents are often effective, rather largeamounts are required if foreign materials enter the system, and suchlarge amounts often destroy the effectiveness of the oil and waterrepellents. If these nonionic agents are generalized by the formulaRO(CH CH O) H, were R is the hydrophobic hydrocarbon group, it has beenfound that compounds where x is less than ten are sometimes ineffectiveas pad bath stabilizers. On the other hand, when x is 20 or 30, thecompounds are quite effective as pad bath stabilizers but quite equallyeffectively destroy oil repellency on the treated fabric at the requiredconcentrations.

It has now been quite unexpectedly found that compounds of the structurewherein n is from 12 to 18, the sum of x and y is from to 20, and eachof x and y is at least 1, and Z is either chloride or acetate, are quiteeffective stabilizers for pad baths containing fluorinated oil and waterrepellents based on fluorinated polymers of CH =C(CH )CO CH CH R;, ashereinabove described, without adversely affecting oil repellency of thefabrics. Moreover, on a comparative basis of ethylene oxide units, thecompounds of this invention are superior stabilizing agents to thosepreviously used in the art. The preferred agents are those where n is18, the sum of x and y is 15, and Z is chloride, namely CHzCHzO) xH ianN -HC1, x+y=15 (CHzCHzObH These useful compounds are the hydrochlorideand acetate salts of the amines CH CHzO),H

CuH2u+1N which are derived from fatty amines C H NH by reaction withethylene oxide. A number of such free amine products are commerciallyavailable under the trade name Ethomeen (manufactured by the ArmourIndustrial Chemical Company). These products are sold containing varyingamounts of ethylene oxide and based on amines produced from cocoa acids,tallow acids, and commercial Stearic acid, i.e., containing 12 to 18carbons. The hydrochloride and acetate salts are readily prepared byneutralizing the free amines with hydrochloric acid and acetic acid bymethods well known to those skilled in the art. For example, a waterdispersion of the free amine is prepared, followed by adding asufiicient quantity of either hydrochloric or acetic acid to neutralizethe amine. The solution is then heated to C. until a clear solution isobtained.

Both the size of the alkyl group, hence the value of n, and the numberof ethylene oxide groups attached to nitrogen, hence the values of x andy and their sum, are critical in this invention. If n is less than 12,the compounds lose their stabilizing effect. Products wherein n isgreater than 18 are not readily available. If each of x and y is not atat least one and their sum is less than 10, the compounds also losetheir stabilizing effect. If the sum of x and y is greater than 20, theoil and Water repellency is seriously decreased. Furthermore, sinceoiland water-repellent baths are acidic, the hydrochloride and aceticsalts are required, since the basic free amines, if used directly, wouldneutralize the acid in the bath forming a salt, and thus destroy thenecessary acid conditions of the pad bath. It is not presentlyunderstood why these compounds are useful while others based on ethyleneoxide are not.

The amount of the above amine hydrochloride compounds required to obtainstable pad baths can vary from situation to situation, depending onwhich and how much foreign agents are entering the system. In mostcases, however, about 0.2% by weight or more, based on the weight of thesolids of the fluoropolymer and non-fluorinated vinylidene polymermixture making up the oil and water repellent is usually satisfactory.Larger amounts are occasionally necessary but, in general, 13% by weighton weight of polymer solids should not be exceeded due to the adverseeffect on oil and water repellency. The most preferred range ofconcentration of stabilizer is from about 1.0% to about 5.0% by weight,based on the weight of the oiland water-repellent polymer solids.

The typical pad bath contains many active ingredients other than the oiland water repellents discussed above. For example, such baths usuallycontain additional water repellents, such as Phobotex f/t/c, awater-insoluble melamineformaldehyde condensation product which containsparafiin wax. The pad bath may also contain one or more of the followingreagents: crease resistance resins such as Aerotex MW, a modifiedmelamineformaldehyde condensate, and dimethylolethylene ureas; permanentpress resins such as 1,5-dimethylol-3,4-dihydroxyethylene ureas asdescribed in US. Patent 3,049,446; fabric softeners such asN-methylolstearamide and polyethylene emulsions; sewing lubricants suchas polyethylene emulsions; antistatic agents such as fatty alcoholphosphates and alkylarylsulfonate salts; hand modifiers such as acrylicresins or polyvinyl acetate; and dispersing agents and catalysts asrequired by the individual constituents.

Representative examples illustrating the present invention follow. Partsand percentages are by Weight unless specified otherwise.

EXAMPLE 1 Two compounds given in Table I below were added to a 13.5%active ingredient dispersion of a fluorinated oiland water-repellentpolymer mixture in water containing about 5%, based on the weight ofpolymer solids, of dimethyloctadecylamine acetate. The polymer mixtureconsisted of 40 parts of fluorinated polymer containing 97.5%fluorinated monomer units derived from a mixture of the structurewherein R, is a perfluoroalkyl group containing from 6 to 14 carbonatoms, 2.0% n-butyl acrylate and 0.5% N-methylolacrylamide as describedin Example 1A of Belgian Patent 645,697, and 60 parts of a vinylidenepolymer containing about 97.7% 2-ethylhexyl methacrylate, 0.5

ethylene dimethacrylate and 1.8% N-methylolacrylamide, as described inFrench Patent 1,414,110, Example 4. The concentration of added compoundin each test listed in Table I below was 3.7% based on the above polymersolids. Each dispersion, stabilized with the indicated stabilizer, wasthen divided into three parts. To one part of the dispersion, analkylbenzenesulfonic acid salt. Iberterge was added in suflicientquantity to provide one molecular equivalent for each mole ofdimethyloctadecylamine acetate present, an amount suflicient to cause 6EXAMPLE 3 Five pad baths containing the active ingredients enumerated inTable III below were prepared. Baths 1 through 4 were preparedcontaining the stabilizer of the present invention. Bath 5 was preparedusing the stabilizers heretofore used in the prior art. Theconcentration in is the weight of the stabilizer based on the weight ofthe oiland water-repellent polymer solids in the bath composition.

coagulation of the dispersion. To the second part sufiicient 1O zincnitrate was added to cause complete coagulation of the above polymericdispersion in the absence of the added TABLE III compound. To the thirdpart suflicient sodium bicarbonate Percent on Weight of Bath was addedto cause complete coagulation in the absence Cllmpment of the addedcompound. These compounds are represen- Water repellent A 1. 44 1. 44tatrve of the materials present in commercial pad bath s Waterrepellent]; 2 M M M which cause coagulation. The dberterge and sodiumbicarbonate are representative of impurities carried into (03203103111pad baths by the fabrics. Zinc nitrate is a typical curing CrsHznN .11 165 mm 0,01 0,013 catalyst for water repellents such as the melamineform-(3-4) (1-4) (3-7) (3-7) (CH2CH20)yH aldehyde condensates.

These mixtures were evaluated after 20 hours and given an arbitrarynumber rating from zero (no coagulation) C9H19C5H O(CH2CHzO)mH 0. 026

U (a 2) to 5 (complete coa ulation). The plus and minus signs are 26CQHWOGHAO (CHZGHzOMH O 026 used to indicate greater or less coagulationthan the num- 3.2

Oil/water repellent 3 3.6 4.8 3.6 3.6 6.0 ber 1nd1cates. The results areshown in Table I below. Washwear Resin A 4 4 8' 4 8' 4 8. 4 8. 4

%asg-wear gesin g 5. 7

as -wear esin 0 8.4 8.4 8.4 8.4 TABLE I Curing Catalyst 1 2.88 2.88 2.882.88 2.88 Surface Active Agent: 1 Water repellent A: 67 parts Phobotexf/t/c and 25 parts Catalyst RB. Phobotex f/t/c is a 25% petroleumwax-75% reaction product of (CHZCHZO) hexamethoxymethylmelamine +3 molesstearic acid +1 mole triethanolat n y Ralilng mine plus acetic acid, asmore fully described in U.S. Patent 2,783,231. n ZlrH Catalyst RB is 2parts aluminum glycollate plus one part glycollic acid. Water repellentB: a 27% active ingredient dispersion of solids in 2 2 water, the solidsbeing 46% paraffin wax, 46% reaction product ofhexaglethloxymethyfielaii aying +ilhrnol'es Claeheinici acid, t4?dimethyloctaecy amine ace a e. ime y te ra ecy am ne ace a e. 11 +1! ZIber- K QZ NaHCOa 3 Oil/water repellent? a 13.5% active ingredientdispersion of polymer terse mixture consisting of 40 parts fluorinatedpolymer containing 97.5% units derived from a mixture of fluorinatedmonomers CH2=0(CH )CO2CH2- it 7,{" 15 C1 1 CHZRf, wherein R: is aperfluoroalkyl having from 6 to 14 carbon atoms, 00mml 5 C1 5 4 2.0%n-butyl acrylate, and 0.5% N-methylolacrylamide, and 60 parts of 10 C1 1a vinylidene polymer consisting of 99.5% 2-ethylhexyl methaerylate, and

18. 1. 15 6O2CCH: 3 0.5% N -methylolacrylamide, Example 1B, BelgianPatent 645,697.

COCO?! 5 floiccHfl 3 Wash'wear Resin A: Permatresh 197-a dimethylolcyclic nitrogen 10 60200113 3'- compound 15 C1 5 Wash-wear Resin B:Durazone DC-a urea formaldehyde adduct. 10 C1 B Wash-wear Resin 0:"Aerotex MW"a modified melamineformalde- 5 C1 3 hyde condensate. 2 C1 5Curing Catalyst: Magnesium chloride.

l Cocoa=alkyl groups contain an average of twelve carbons.

From the above table, it can be seen that the value of the sum of x andy is critical to the stabilizing effect of the salt.

EXAMPLE 2 In a manner similar to that of Example 1, the preferredcompound of the present invention was compared with a series of othersurface active agents derived from ethylene oxide as to the ability ofthese agents to stabilize oiland water-repellent compositions in thepresence of reagents which normall cause coagulation. The resultsobtained are shown below in Table II.

TABLE II Stability Rating Surface Active Compound Each bath was appliedto navy blue and tan cotton fabrics using one dip and one nip at F. Thewet pickup for the navy blue fabric was 45%; for the tan fabric 50%. Thefabrics were then dried at 250 F. and cured for 1.5 minutes at 340 F.The fabrics were then tested for oil and water repellency initially,after three standard launderings, and also after one dry cleaning, withthe results shown in Table IV below.

The water repellencies of the treated fabric samples were measured byusing A.A.T.C.C. Standard Test Method 22-1952 of the AmericanAssociation of Textile Chemists and Colourists (ASTM D-583-63). A ratingof 100 denotes no water penetration or surface adhesion; a rating ofdenotes slight random sticking or wetting, and

so on.

The oil repellency test used in the following examples comprises placinga drop of test solution carefully on the textile on a flat horizontalsurface. After three minutes, any penetration or wicking into the fabricis noted visually. To aid in the observation, the test solution cancontain a small amount of oil-soluble blue dye to improve visibility.The nature of the test solutions is shown below. Nujol, of course, is apurified petroleum oil. Anything with a rating of five or greater isgood or excellent, whereas anything with a rating of two or over can beused only for certain purposes. As an example of the rating method, if atreated fabric repels solution No. 6 listed below, but not the seventhsolution, its rating is 6.

7 Test solution: Oil repellency rating n-Heptane 9 n-Octane 8 n-Decane 7n-Dodecane 6 n-Tetradecane 50-50 n-hexadecane-Nujol 4 25-75hexadecane-Nujol 3 Nujol 2 Wet by Nujol 0 A standard laundering consistsof immersing the fabric sample for 40 minutes with agitation in water atfrom 60 C. to 100 C. containing 0.1% by weight of a neutral chip soapwith 0.05% of soda ash. The fabric sample is thereafter rinsed threetimes in 60 C. water, then the sampleis centrifuged for five minutes,and finally pressed 30 seconds on each face at 300 Fri-20 F.

The dry cleaning consists of agitating the fabric sample for 20 minuteswith tetrachloroethylene at room temperature and then drying the fabricby first centrifuging one minute followed by drying for five minutes at160 F. in the tumble dryer. The fabrics were then pressed seconds oneach face at 300 F.: F.

TABLE IV.REPELLENCIES Pad Bath Oil 3 SL DC Water 3 SL* DC InitialInitial Navy Blue:

'SL=Standard Laundering; DC=dry cleaning.

As can be seen from the results set forth in Table IV above, thestabilizing compound of this invention does not destroy theeffectiveness of the oil and water repellent.

EXAMPLE 4 Two pad baths were prepared with the formulations set forth inTable V below.

1 Same as Water Repellent A, Example 3, except that 62.5 parts Phobotexf/t/c and 37.5 parts "Catalyst BB were used.

1 An 11.6% active ingredient dispersion of equal weights of thefluorinated polymer and vinylidene polymer of Example 1.

3 Indicates weight based on the weight of the oiland water-repellentpolymer solids.

A black fabric, dyed with a sulfur black dye and containing a highconcentration of salts, was padded with bath 1 in a commercial mill at arate of yards per minute at about 40% pickup. A total of 17,400 yardswas padded without any difiiculty. The resulting fabric had Waterrepellencies of 80 and oil repellencies of 7 to 8.

When the same fabric was padded with bath 2 under identical conditions,pad-roll buildup began after a few hundred yards had been padded and therun had to be stopped after about 3,000 yards because the pad-rollscould no longer be kept free of intolerable pad-roll buildup.

8 EXAMPLE 5 A 13.5% active ingredient dispersion of a fluorinated oilandwater-repellent polymer mixture in water is prepared containing about5%, based on the weight of the polymer solids, of dimethyloctadecylamineacetate. The polymer mixture consists of 40 parts fluorinated polymercontaining approximately 75% R being a mixture of C to C fluorocarbonalkyl groups, approximately 25 approximately 0.25% CHFC(CH )CO CH CH OH,and approximately 0.25% CHFCHCONHCH OH, and 60 parts of a vinylidenepolymer containing about 97.5% 2-ethylhexyl methacrylate, 0.5% ethylenedimethacrylate, and 2.0% N-methylolacrylamide. The fluorinated polymeris prepared by aqueous polymerization techniques well known to thoseskilled in the art. A polymerization initiator such asazobis(isobutyramidine)dihydrochloride is used and the molecular weightof the polymer is controlled by use of chain transfer agents such asdodecyl mercaptan.

Two pad baths, similar to bath Nos. 1 and 2 of Example 4, are prepared,except that the above oil and water repellent is used. Padding resultssimilar to those of Example 4 are observed in that the bath containingCHZCHZO) H raHu J10 (CHZCH20)yH is at least several times more stablethan the bath which did not contain the stabilizing agent of thisinvention.

EXAMPLE 6 Four oiland water-repellent compositions were prepared usingthe following procedure. Dimethyl octadecylamine acetate was dissolvedin water with agitation. Then the monomer CH =C(CH )CO CH CH (CF ),,F,n=6, 8, and 10 in weight ratio of 3:2:1 containing less than 10% n=12and 14, and n-dodecyl methacrylate were added and homogenized with theaqueous solution. A large amount of water in a separate container wasdegassed with nitrogen and boiling, then added to the above monomerdispersion. Dodecyl mercaptan, a chain transfor agent,N-methylolacrylamide, and 2-hydroxyethyl methacrylate were then added inminor amounts, andthe mixture was heated to 60 C. with agitation. Apolymerization initiator azobis(isobutyramidine dihydrochloride) wasadded. The polymerization was initiated and the heating of the mixtureat 60 C. to 70 C. was continued until polymerization was complete (4 to5 hours). The resulting aqueous dispersion contained approximately 25%solids. All four polymers contained approximately 0.25 Nmethylolacrylamide, 0.25 2-hydroxyethyl methacrylate, and 0.04% of theinitiator. The other proportions are shown below:

Each of the four resulting polymer dispersions was blended with thenon-fluorinated copolymer of Z-ethylhexyl methacrylate andN-methylolacrylamide to give four dispersions containing 13.5 solids and40 parts CH =C(CH )CO CH CH (CF F per parts solids.

Two pad baths were prepared from each of these four dispersions, oneseries containing 4.0% on weight of bath (OWB) of the dispersions (0.54%OWB of polymer solids) and the other containing 5.0% OWB of the polymerdispersions (0.675% OWB polymer solids). All baths contained OWB of a27% zinc nitrate solution, 28.0% OWB Permafresh 183, 60% of waterrepellent B of Example 3, and Ethomeen hydrochloride stabilizing agentof the structure CH2CH2O) H OIEHHN -HCl (CH2GH20)yH wherein the sum of xand y is 15. The amount of the stabilizing agent present was 3.9% basedon the weight of the polymer solids.

Permafresh 183 is an aqueous solution (40% solids) of a permanent creaseresin sold by Sun Chemical, believed to have the structure:

Samples of fabrics Chem. 119, a 65/35 Dacron polyester/ cotton poplin(tan) were treated to obtain 50% wet pickup, dried, cured, and testedfor repellencies as described in Example 3. The results are shown inTable VI below.

'HLAD=Home laundering air dry;

HLTD=H0me laundering tumble dry.

The home laundering tests were conducted as follows: A Kenmore washerModel 600 is loaded with a 4-pound load, with 29 g. of "Tide. The washis set at hot (12- minute cycle) and a warm rinse (12 minutes). Thetotal washing and rinsing time is 40 minutes. In the home laundering airdry test (HIAD), the spun dry fabrics are dried at ambient temperatures.In the home laundering tumble dry test (HLTD), the spun dry fabrics aredried at 156 F. to 160 F. in a home drier with tumbling.

The above-described pad bath formulations were stable and resistedcoagulation for long periods of time.

It is to be understood that the preceding examples are representativeand that said examples may be varied within the scope of the totalspecification, as understood by one skilled in the art, to produceessentially the same results.

As many apparently widely difierent embodiments of this invention may bemade without departing from the spirit and scope thereof, it is to beunderstood that this invention is not limited to the specificembodiments thereof except as defined in the appended claims.

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows:

1. In a pad bath used to treat textile fabrics to obtain oil and waterrepellency which contains an aqueous dispersion of a fluorinated oilandwater-repellent polymer and one or more of a permanent press resin, acrease resistance resin, a fabric softener, a hand modifier, anantistatic agent, a curing catalyst and a dispersing agent, some ofwhich are incompatible causing instability of the pad bath, theimprovement comprising adding an effective amount of a stabilizingcompound having the structure omcmoprr CnH2u+lN -HZ CH CHzO) H wherein nis from 12 to 18, the sum of x and y is from 10 to 20 and each of x andy is at least one, and Z is an anion selected from the group consistingof chloride and acetate.

2. The pad bath of claim 1 wherein the stabilizing compound has thestructure CHzCHzO) H Cm m -HC1 CHzCHgO) yH the sum of x and y 'being 15.

3. The pad bath of claim 1 wherein the amount of the stabilizingcompound present is from about 0.2% by weight to about 13% by weightbased on the weight of the polymer solids present.

4. The pad bath of claim 3 wherein the stabilizing compound has thestructure cia eiN the sum of x and y being 15.

5. The pad bath of claim 3 wherein the fluorinated oil and waterrepellent is a mixture of (A) a fluorinated polymer comprising unitsderived from the monomer of CH =C(CH CO CH CH R wherein R is a C to C-perfluoroalkyl, and

(B) a non-fiuorinated polymer comprising units derived from the monomerCH C(CH )CO R, wherein R is an alkyl group having up to 18 carbon atoms.

References Cited UNITED STATES PATENTS 3,256,230 6/ 1966 Johnson et al260900 3,277,039 10/ 1966 Morascia et a1.

3,282,905 11/1966 Fasick et a1. 260900 3,331,812 7/1967 Chai Lee 260-4593,347,812. 10/1967 De Marco et al 260-900 3,350,314 11/1967 Dawtrey eta1. 260-307 3,352,709 11/1967 Gunnar et al 260567.6

MURRAY TILLMAN, Primary Examiner.

H. ROBERTS, Assistant Examiner.

US. Cl. X.R.

